CN101056904A - Polymerization-curable composition - Google Patents
Polymerization-curable composition Download PDFInfo
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- CN101056904A CN101056904A CNA2005800382753A CN200580038275A CN101056904A CN 101056904 A CN101056904 A CN 101056904A CN A2005800382753 A CNA2005800382753 A CN A2005800382753A CN 200580038275 A CN200580038275 A CN 200580038275A CN 101056904 A CN101056904 A CN 101056904A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Eyeglasses (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Optical Filters (AREA)
Abstract
The invention provides a polymerization curing composition, which is formed by matching the specific two-functional monomer which contains a structure that has 2 phenylenes and is bonded by specific groups such as 2, 2-bis(4-methyl propenoyl oxide polyethoxyl phenyl) propane, the polyfunctional polymer monomer with more than three functions such as trimethylol propane trimethacrylate, and the other monomers with a photochromic compound and a specific light stabilizer such as bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate ester by specific proportion respectively; the composition shows the excellent photochromic feature of fading rate and simultaneously gives a solid which has enough anti-drilling processing strength for rimless eyeglasses, and the long-term preservation stability is high.
Description
Technical field
The present invention relates to provide the cured article and the high polymerization-curable composition of storage stability of strength characteristics with excellent photochromic characteristic and excellence.
Background technology
Photochromic glasses are in such the containing outside ultraviolet light-struck room of sunlight, lens are rapidly painted and as sun glasses performance function, do not bring into play functional eyeglasses there being this light-struck fading within doors as the normal transparent glasses, particularly plastic photochromic glasses, demand is in recent years increasing always.
As one of the manufacture method of the Plastic eyeglasses lens with photochromism, knownly make photochromic compound be dissolved in the polymerizable monomer composition and make its polymerization, thereby directly obtain the method (hereinafter referred to as the method for sneaking into) of photochromic lens.This method is to give photochromism in the lens moulding, compares with handling the method for giving photochromism behind the molded lens again, has the advantage that can obtain the photochromism plastic lens step.
Photochromism produces the reversible structural changes by photochromic compound absorption luminous energy and realizes, but for the photochromism plastic lens of using the method for sneaking into to obtain, because photochromic compound is dispersed in the cured article matrix, the photochromic characteristic of therefore relate to color development concentration, the speed of fading is so often can not be given full play to the characteristic that photochromic compound had originally.This be because with solution in compare, freeboard in this matrix is minimum, therefore the structural changes of photochromic compound molecule is restricted easily, and when particularly the high-molecular weight photochromic compound being dispersed in the high cured article matrix of hardness and thermotolerance, this tendency is remarkable.For example, the photochromic compound of molecular weight more than 300 is dispersed in as in the general solidification compound of plastic lens substrate the time, the transformation period of fading elongated significantly sometimes (speed of fading is slack-off significantly) of photochromic compound, the transformation period of fading in the cured article matrix can reach more than 50 times of the transformation period of fading in the solution.
As there not being this problem, promptly have excellent photochromic characteristic and can give hardness and the solidification compound of the photochromism cured article that thermotolerance is high, known have a following polymerization-curable composition (below be also referred to as composition in the past), and this polymerization-curable composition contains: (A) the L scale Rockwell hardness of the polymkeric substance of gained is a polymerizable monomer below 40 during homopolymerization, (B) the L scale Rockwell hardness of the polymkeric substance of gained is the above polymerizable monomer of trifunctional more than 60 during homopolymerization, (C) the L scale Rockwell hardness of the polymkeric substance of gained is two sense polymerizable monomers and (D) photochromic compound (disclosing brochure No. 01/05854 referring to the world) more than 60 during homopolymerization.
Feedstock composition when above-mentioned composition is in the past sneaked into manufactured photochromism plastic lens as employing is very useful, in the time of but the cured article that makes said composition solidify gained will being used for nearest popular no-frame glasses (bracket component that is used for the hook lens during use and lens by these lens tighten up a screw the glasses that do not have the edge that the fixed hinge is connected) with screw hole, hole to add with rig as can be known and can cause cracking man-hour, even or boring adds and man-hour do not occur special problem, in case applying load also can produce the problem of the lens breakage of fixed part on the fixed bracket component.
Therefore, for the reason of finding out that intensity after this boring adds man-hour or processing (below be also referred to as anti-boring processing intensity) reduces, ratio of components to above-mentioned composition is in the past studied, the result distinguishes: when particularly aforementioned " the L scale Rockwell hardness of the polymkeric substance of gained is the above polymerizable monomer of trifunctional more than 60 during homopolymerization " (below's be also referred to as polyfunctional monomer) addition was big, the anti-boring processing intensity of cured article significantly reduced.Expect thus can reducing the polyfunctional monomer amount, but obviously having following balance relation:, then be difficult to obtain excellent photochromic characteristic if make the addition of polyfunctional monomer very few in order to improve anti-boring processing intensity.Carried out further research based on this understanding, found that the cooperation ratio that makes above-mentioned polyfunctional monomer contained in the polymerization-curable composition is in specific scope, and contain the specific aggregation monomer of specified quantitative as the photochromism solidification compound of two sense polymerizable monomers (below be also referred to as improve composition), can satisfy above-mentioned characteristic, thereby proposed scheme (opening the 2005-68192 communique referring to the spy) before this, above-mentioned specific aggregation monomer has two phenylenes and carries out the bonded structure by special groups.
Above-mentioned improvement composition has the cured article of following advantageous feature.That is, give following cured article: the transformation period of fading of the photochromic compound in the cured article is in 30 times of the transformation period of fading of this photochromic compound in solution, and the tensile strength of the following definitions of this cured article is more than the 20Kgf.
Wherein, transformation period of fading is meant that carrying out rayed becomes when stopping rayed behind the color development state photochromic compound, 1/2 required time the when absorbancy at above-mentioned maximum wavelength place is reduced to color development is the finger target value that becomes the speed of fading of one of most important properties in the photochromic characteristic.The transformation period of fading of the photochromic compound in the base material is in 30 times of the transformation period of fading of this photochromic compound in solution, in preferred 10 times, more preferably in 7 times, in preferred especially 5 times, means to have excellent photochromic characteristic.Moreover there is no particular limitation for the solvent of above-mentioned photochromic compound solution, but as standard solvent, can enumerate glycol dimethyl ether.In addition, if with fading the transformation period in the absolute value representation cured article, then it is in 4 minutes, is preferably in 2 minutes.
In addition, tensile strength is the index of anti-boring processing intensity, is the tensile strength when operating in the following manner: for thickness is 1～5mm, as can crooked plate-like test film, its main surface area being 10～40cm
2Test film, with distance by near its center of gravity or the center of gravity and two intersection points of the arbitrary line of transversal test film and substrate periphery separately 2 on this straight line of 4mm inboard respectively as the center, on test film, get out the hole of two diameter 2mm φ by boring processing, then in two borings that obtain respectively through diameter be the rod of the stainless steel of 1.6mm φ, then these two rods are separately fixed on the last lower clamp of tensile testing machine, carry out tension test with the speed that 5mm/ divides.Moreover, in the tensile strength test shown in the above-mentioned definition, the destruction of test film usually occur in that rig holes near, for the material that uses as eyeglass lens usually, tensile strength is subjected to the influence of base material shape hardly.In addition, the shape and the size that are processed to the eyeglass lens of common type of service front and back are in the scope of above-mentioned test film, and therefore above-mentioned tensile strength also directly becomes the index of the anti-boring processing intensity of eyeglass lens.But, when above-mentioned tensile strength is processed the index of intensity as the anti-boring of eyeglass lens, eyeglass lens for the shape that is processed into actual use, suitable to a boring in two holes, make its position and no circle frame is installed (promptly, with hinged bracket component) time the position roughly the same, carry out tension test.
The tensile strength that can be used for no-frame glasses is more than the 20Kgf, tensile strength is that 20Kgf is when above, corresponding to no-frame glasses in monitor uses, demonstrate good result and with the optional position of revolution of 2100rpm at base material on adopt the rig processing drill diameter 2mm φ that (, adopts 1 hole/1 second with interior speed) tempestuously as standard the hole time do not produce big crackle (crack length is in 0.4mm).
Improve composition and suit as the cured article of no-frame glasses with the photochromism plastic lens, but said composition is made further research, the result exists the problem that storage stability requires further improvement as can be known.Promptly, when though the polymerizable monomer itself that uses in the above-mentioned improvement composition is for example preserved under low temperature (below 10 ℃), even preserving 1 year quality can not reduce yet, but shown and remained to be improved part below the existence: if photochromic compound (pigment) mixing is preserved, pigment deterioration then, composition generation xanthochromia.When using xanthochromic composition to make photochromic lens, resulting lens are just painted under the non-irradiated state of light.
Summary of the invention
Therefore, the object of the present invention is to provide the storage stability that improves above-mentioned improvement composition,, can bring into play the composition that improves the advantageous feature that composition had even the prolonged preservation quality does not reduce yet.
The present inventor furthers investigate at this problem.It found that by cooperate specific photostabilizer with specific ratio in polymerizable monomer composition, can solve above-mentioned problem, thereby finish the present invention.
That is, the present invention relates to polymerization-curable composition, it is characterized in that containing:
(I): by multifunctional polymerization monomer 1～15 quality % of two sense polymerizable monomers, 10～80 quality % of (I-1) following formula (1) expression, (I-2) following formula (2) expression and (I-3) above-mentioned (I-1) and (I-2) polymerizable monomer composition 100 mass parts formed of in addition polymerizable monomer 5～89 quality %
(II): photochromic compound 0.001～5 mass parts and
(III): by having 2,2,6, photostabilizer 0.001～0.5 mass parts that the compound of 6-tetramethyl--4-piperidyl skeleton constitutes, especially preferably photostabilizer 0.001～0.5 mass parts that constitutes by the compound of following formula (3) expression.
In the formula, R
1And R
2Be hydrogen atom or methyl independently of one another, R
3And R
4Be the alkyl of hydrogen atom or carbon number 1～2 independently of one another ,-X-group be usefulness-O-,-S-,-S (=O)
2-,-C (=O)-O-,-CH
2-,-CH=CH-or-C (CH
3)
2The group of-expression, m and n are the integer that makes m+n=2～30 independently of one another }.
In the formula, R
5Be hydrogen atom or methyl ,-R
6-group is usefulness-CH
2CH
2O-,-CH
2CH (CH
3) O-or-C (=O) CH
2CH
2CH
2CH
2CH
2The group that O-represents, R
7Be organic residue of 3～6 valencys, a is 0～3 integer, and b is 3～6 integer }.
In the formula, R
8, R
9Be hydrogen atom or methyl independently of one another, n is 5～12}.
Embodiment
Polymerization-curable composition of the present invention contain specific polymerizable monomer composition (below be sometimes referred to as monomer composition) (I), photochromic compound (II) and specific photostabilizer (III).By using above-mentioned certain monomers composition (I) as the polymerizable monomer composition, the anti-boring processing intensity of cured article improves, and it is good that photochromic characteristic becomes.Below, at first above-mentioned polymerizable monomer composition (I) is described.
The monomer composition that uses among the present invention (I) comprises following compositions (I-1), (I-2) and (I-3) (these compositions add up to 100 quality %).
(I-1) composition that constitutes by two sense polymerizable monomers of above-mentioned formula (1) expression (below be also referred to as specific two functional monomers)
(I-2) composition that constitutes by the multifunctional polymerization monomer of above-mentioned formula (2) expression (below be also referred to as specific polyfunctional monomer)
(I-3) above-mentioned (I-1) and (I-2) in addition polymerizable monomer (below be also referred to as other monomers).
In above-mentioned formula (1) to formula (2), R
1, R
2And R
5Represent hydrogen atom or methyl independently of one another, R
3And R
4The alkyl of representing hydrogen atom or carbon number 1～2 independently of one another, i.e. methyl or ethyl.In addition ,-the X-group be usefulness-O-,-S-,-S (=O)
2-,-C (=O)-O-,-CH
2-,-CH=CH-or-C (CH
3)
2The group of-expression ,-R
6-group is usefulness-CH
2CH
2O-,-CH
2CH (CH
3) O-or-C (=O) CH
2CH
2CH
2CH
2CH
2The group that O-represents.In addition, R
7Be organic residue of 3～6 valencys, the alkyl of preferred 3～6 valencys, the most preferably alkyl of 3 valencys.As R
7, if preferred group is shown, can enumerate group (CH
2)
3C-C
cH
2c+1(wherein, c is 1～3 integer).If list the concrete structure of these groups, then can be listed below structure.
In addition, m and n represent to make the integer of m+n=2～30 independently of one another, and a and b represent 0～3 integer and 3～6 integer respectively.
In specific two functional monomers that constitute mentioned component (I-1), m and n are that m+n was less than 8 o'clock in the above-mentioned formula (1), be equivalent to the above-mentioned world and disclose (C) composition in the disclosed composition in the past in No. 01/05854 brochure, i.e. the L scale Rockwell hardness of the polymkeric substance of gained is the contained polymerizable monomer of two sense polymerizable monomers more than 60 during homopolymerization.In addition, m+n is 8 when above, is equivalent to (A) composition in the composition in the past, i.e. the L scale Rockwell hardness of the polymkeric substance of gained is the polymerizable monomer below 40 during homopolymerization.
Moreover, L scale Rockwell hardness described herein is the value of determining by JIS K7202, specifically following value: the pressure head that uses the steel ball by diameter 6.350mm to constitute on the surface of cured article test film, apply the standard load of 10Kgf, then apply the test load of 60Kgf, turn back to standard load again, the difference h (mm of unit) of the pressure head immersion depth under being loaded from the front and back standard twice by this calculating formula of 130-500h obtains.
In specific two functional monomers of (I-1) composition, consider easy acquisition, if the monomer that particular instantiation is preferably used, then can enumerate 2, two [4-(methacryloxy polyethoxye) phenyl] propane (mean value of m+n is 2 monomer) of 2-, the same (mean value of m+n is 2.6 monomer), the same (mean value of m+n is 4 monomer), the same (mean value of m+n is 10 monomer), the same (mean value of m+n is 30 monomer), 2, two [4-(acryloxy polyethoxye) phenyl] propane (mean value of m+n is 4 monomer) of 2-, 2, two [4-(methacryloxy the gathers propoxy-) phenyl] propane (mean value of m+n is 4 monomer) of 2-, the same (mean value of m+n is 10 monomer), two [4-(methacryloxy polyethoxye) phenyl] methane (mean value of m+n is 4 monomer), two [4-(methacryloxy polyethoxye) phenyl] sulfone (mean value of m+n is 4 monomer) etc.These monomers can use separately, also can two or more mixing use.
As the content of composition (I-1) in monomer composition (I), be benchmark with the total mass of whole monomer components contained in the said composition (I), be necessary for the scope of 10～80 quality %.When this composition contain quantity not sufficient 10 quality % the time, can not obtain needed intensity of no-frame glasses or toughness.On the other hand, when surpassing 80 quality %, too high to the viscosity of biding one's time as composition, be difficult to handle, and too upright and outspoken as cured article to the structure of biding one's time, therefore the molecular motion of photochromic compound is restricted, can not obtain gratifying photochromic characteristic (transformation period of fading is slack-off).For the foregoing reasons, the content of composition (I-1) is preferably 20～60 quality % under said reference.
The composition (I-2) that is made of the polyfunctional monomer shown in the above-mentioned formula (2) is equivalent to the above-mentioned world and disclose (B) composition in the disclosed composition in the past in No. 01/05854 brochure, i.e. the L scale Rockwell hardness of the polymkeric substance of gained is the polymerizable monomer more than the trifunctional more than 60 during homopolymerization.By using this polymerizable monomer, can obtain particularly is the cured article of the photochromic characteristic excellence of representative with the transformation period of fading.In above-mentioned specific polyfunctional monomer, consider from easy acquisition aspect, if the monomer that particular instantiation is preferably used then can be enumerated trimethylolpropane trimethacrylate, Viscoat 295, the tetramethylol methane trimethacrylate, the tetramethylol methane triacrylate, trimethylolpropane trimethacrylate, tetramethylol methane tetramethyl-acrylate, the tetramethylol methane tetraacrylate, trimethylolpropane tris glycol trimethacrylate, trimethylolpropane tris glycol triacrylate, the ethoxylation tetramethylol methane tetraacrylate, ethoxylation tetramethylolmethane tetramethyl-acrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate, caprolactone (カ プ ロ ラ Network Application) modification dimerization (TriMethylolPropane(TMP)) tetraacrylate, caprolactone modification dimerization (TriMethylolPropane(TMP)) tetramethyl-acrylate, caprolactone modification dipentaerythritol six acrylate etc.These monomers can use separately separately, also can two or more mixing use.
As the content of specific polyfunctional monomer in composition of the present invention of composition (I-2), be benchmark with the total mass of whole monomer components contained in the monomer composition (I), be 1～15 quality %, be preferably the scope of 3～10 quality %.When composition (I-2) contain quantity not sufficient 1 quality % the time, can not obtain enough photochromic characteristics, on the other hand, when surpassing 15 quality %, can not obtain the required intensity of no-frame glasses (toughness).The preferred content of composition (I-2) depends on the content as specific two functional monomers of composition (I-1), during composition (I-1) less than 40 quality %, the content that preferably makes composition (I-2) is 1～10 quality %, the content of composition (I-1) is 40 quality % when above, and the content that preferably makes composition (I-2) is 3～15 quality %.Thus, can obtain the especially cured article of excellence in the equilibrium of photochromic characteristic and intensity.
The monomer composition that uses in the polymerization-curable composition of the present invention (I) contains the mentioned component (I-1) of 5～89 quality % and (I-2) in addition polymerizable monomer composition (below be also referred to as other monomers).As this " other monomers ", preferably using L scale Rockwell hardness is above polymerizable monomer (the multifunctional polymerization monomer) monomer in addition of trifunctional more than 60.Preferred for example use disclose (A) composition that uses in the disclosed solidification compound (composition in the past) in No. 01/05854 brochure as the above-mentioned world and reaches (C) the illustrated following monomer of composition (but except specific two functional monomers).
If particular instantiation as the preferred monomers of (I-3) composition, can be used the polyethylene glycol methacrylate-styrene polymer of the molecular-weight average 526 that is equivalent to (A) composition, the polyethylene glycol methacrylate-styrene polymer of molecular-weight average 360, the methyl ether polyethylene glycol methacrylate-styrene polymer of molecular-weight average 475, the methyl ether polyethylene glycol methacrylate-styrene polymer of molecular-weight average 1000, the polypropylene glycol methacrylic ester of molecular-weight average 375, the polypropylene glycol methacrylic ester of molecular-weight average 430, the methacrylic acid stearyl ester, lauryl methacrylate(LMA), diglycidyl ether of ethylene glycol, the propylene glycol glycidyl ether, Viscoat 335HP, nine glycol diacrylates, the polyoxyethylene glycol allyl ethers of molecular-weight average 200, the polyoxyethylene glycol allyl ethers of molecular-weight average 1500, the methoxy poly (ethylene glycol) allyl ethers of molecular-weight average 350, the methoxy poly (ethylene glycol) allyl ethers of molecular-weight average 550, the methoxy poly (ethylene glycol) allyl ethers of molecular-weight average 1500, the methoxy poly (ethylene glycol) polypropylene glycol allyl ethers of molecular-weight average 620 etc.
In addition, can use the diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, nine glycol dimethacrylates, nine polypropylene glycol dimethacrylates, the ethylene glycol bis glycidyl methacrylate, 1 that are equivalent to (C) composition, 4-butylene glycol dimethacrylate, 1,9-nonanediol dimethacrylate, neopentylglycol dimethacrylate etc.
In addition, as " other monomers ", can use as being equivalent to (A) composition and (C) the multi-allylation compounds such as Phthalic acid, diallyl ester, diallyl isophthalate, tartrate diallyl of the polymerizable monomer beyond the composition; Acrylic compound of glycidyl acrylate, glycidyl methacrylate, methyl acrylate, methyl methacrylate, benzyl methacrylate and so on and methacrylate compound; The vinyl compound of vinylbenzene, chlorostyrene, vinyl toluene, vinyl naphthalene, α-Jia Jibenyixierjuwu, bromostyrene, Vinylstyrene and so on etc.
And, also preferred 2～6 officials energy polymerizability urethane oligomer, 2～6 officials energy polymerizability polyester oligomer of using.
2～6 officials can polymerizability urethane oligomer in by various vulcabond, polyvalent alcohol synthetic polyurethane skeleton on the remaining isocyanate group addition hydroxyl acrylic or hydroxymethyl vinylformic acid form.Object lesson as vulcabond, can enumerate tolylene diisocyanate, 4,4-diphenylmethanediisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methylene-bis (4-cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate etc.In addition, object lesson as polyvalent alcohol, can enumerate polypropylene oxide glycol, copolymerization epoxy ethane-epoxy propane glycol, poly-1,4-butylene oxide ring glycol, ethoxylation dihydroxyphenyl propane, ethoxylation bisphenol S the spiroglycol, caprolactone (カ プ ロ ラ Network Application) modification glycol, carbonic ether glycol, polyester glycol, glycol ether, triglycol, 1,6-hexylene glycol, TriMethylolPropane(TMP), ethoxylated trimethylolpropane, tetramethylolmethane etc.
2～6 officials can polymerizability polyester oligomer be condensation acrylic or methacrylic acid and forming on the hydroxyl remaining in by various polyvalent alcohols and polyprotonic acid synthetic polyester backbone.
As the object lesson of polyvalent alcohol, can enumerate and the identical various polyvalent alcohols of polyvalent alcohol that in above-mentioned 2～6 officials energy polymerizability urethane oligomer, illustrate, as the object lesson of polyprotonic acid, can enumerate Tetra hydro Phthalic anhydride, hexanodioic acid, trimellitic acid etc.
Polymerization-curable composition of the present invention contains photochromic compound as composition (II).As photochromic compound, can use for example known photochromic compounds such as chromene compounds, fulgenimide acylimino, spiral shell piperazine compound, be not particularly limited.Using molecular weight is more than 200, particularly during the high molecular photochromic compound more than 500, effect of the present invention shows when particularly forming cured article that the effect of good photochromic characteristic is remarkable, the therefore preferred photochromic compound that uses this molecular weight.In these photochromic compounds, the photochromic characteristic of chromene compounds is than other serial chemical combination object heights, and color development concentration, the speed of fading etc. are also excellent, therefore especially preferably use.In above-mentioned chromene compounds, as particularly preferred compound, can the following formula of illustration (4)
In the formula, R
10, R
11, R
12, R
13, R
14, R
15, R
16, R
17, R
18, R
19Represent hydrogen atom, alkyl, alkoxyl group, aralkoxy, substituted-amino, cyano group, halogen atom, aralkyl independently of one another and can have substituent aryl, morpholino, piperidino-(1-position only), Piperazino nitrogen substituted cyclic compounds, particularly R such as (piperazino)
18And R
19Can be interconnection and form and can have substituent cycloalkyl, in addition, A
1And A
2Represent hydrogen atom independently of one another, can have substituent aryl } shown in indeno naphthopyrans compound, following formula (5)
In the formula, R
20, R
21, R
22, R
23, R
24, R
25Represent hydrogen atom, alkyl, alkoxyl group, aralkoxy, substituted-amino, cyano group, halogen atom, aralkyl independently of one another and can have nitrogen substituted cyclic compounds such as substituent aryl, morpholino, piperidino-(1-position only), Piperazino, in addition, A
3And A
4Represent hydrogen atom independently of one another, can have substituent aryl } shown in naphthopyrans compound and following formula (6)
In the formula, R
26, R
27, R
28, R
29, R
30, R
31Represent hydrogen atom, alkyl, alkoxyl group, aralkoxy, substituted-amino, cyano group, halogen atom, aralkyl independently of one another and can have nitrogen substituted cyclic compounds such as substituent aryl, morpholino, piperidino-(1-position only), Piperazino, in addition, A
5And A
6Represent hydrogen atom independently of one another, can have substituent aryl } shown in the naphthopyrans compound.
If the preferred photochromic compound that uses, the then compound that can be listed below among particular instantiation the present invention.Moreover, though these compounds can use separately, the common tone when regulating color development, often other photochromic compounds (comprising following compound and photochromic compound in addition) with one or more use.
Molecular weight 515
Molecular weight 741
Moreover, in the compound of above-mentioned formula (4), (5), (6) expression, A in the special preferred formula (4)
1, A
2In at least one compound, formula (5) for the aryl that replaced by dialkyl amido in A
3, A
4In at least one compound, formula (6) for the aryl that replaced by dialkyl amido in A
5, A
6In at least one compound for the aryl that replaced by dialkyl amido because the degradation inhibiting effect that the photostabilizer of above-mentioned formula (3) expression produces is especially big.
The amount of photochromic compound in polymerization-curable composition of the present invention is necessary for 0.001～5 mass parts with respect to polymerizable monomer composition 100 mass parts of above-mentioned (I).The content of photochromic compound during less than 0.001 mass parts, can not obtain enough color development concentration under said reference, be difficult to make it to disperse equably when surpassing 5 mass parts.From color development concentration and uniformly dispersed viewpoint, the content of photochromic compound is preferably 0.01～2 mass parts under said reference.
Polymerization-curable composition of the present invention contains by having 2,2,6, and the photostabilizer that the compound of 6-tetramethyl--4-piperidyl skeleton constitutes is as composition (III).By containing this composition (III), storage stability improves, even the prolonged preservation photochromic compound can deterioration yet, can bring into play and improve the advantageous feature that composition had originally.Moreover the compound outside stating in the use is difficult to obtain enough stabilization effects during as photostabilizer.If the preferred photostabilizer of illustration can enumerate two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, two (1-octyloxies-2,2,6,6-tetramethyl--4-piperidyl) sebate, 1-[2-{3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyloxy } ethyl]-4-{3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyloxy }-2,2,6, the 6-tetramethyl piperidine, 4-benzoyloxy-2,2,6, the 6-tetramethyl piperidine, methyl (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, 1,2,2,6,6-pentamethyl--4-piperidino methyl acrylate, it is poly-that [{ 6-(1,1,3, the 3-tetramethyl butyl) amino-1,3,5-triazines-2,4-two bases } { (2,2,6,6-tetramethyl--4-piperidyl) imino-} hexa-methylene { (2,2,6,6-tetramethyl--4-piperidyl) imino-}] etc.Moreover in these compounds, the photostabilizer that is made of the compound shown in the above-mentioned formula (3) obtains easily, the effect height, and is easy to handle, and is preferred especially from these aspects.If the typical example of the compound of the above-mentioned formula of illustration (3) expression then can enumerate two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) sebate etc.
The amount of composition (III) in solidification compound of the present invention is necessary for 0.001～0.5 mass parts with respect to polymerizable monomer composition 100 mass parts of above-mentioned (I).The content of composition (III) during less than 0.001 mass parts, can not obtain enough anti-pigment degradation effects under said reference, photostabilizer itself is painted when surpassing 0.5 mass parts, so may be painted when forming cured article.In order to bring into play the abundant effect of effect of the present invention and photostabilizer, the content of photostabilizer is preferably 0.005～0.3 mass parts under said reference.
In order to improve the weather resistance of photochromic compound, improve color development speed, the speed of fading and formability, can in polymerization-curable composition of the present invention, in the scope of not damaging effect of the present invention, further add various additives.As the additive of preferred use, for example can enumerate tensio-active agent, oxidation inhibitor, free radical scavenger, UV light absorber, releasing agent, anti-coloring agent, static inhibitor, fluorescence dye, dyestuff, pigment, spices, be used to silane coupling agent that improves the hard coat adaptation etc.
As above-mentioned tensio-active agent, can use any kind in nonionic class, anionic species, the cationic, as oxidation inhibitor, free radical scavenger, UV light absorber, preferably use hindered phenol antioxygen, phenols free radical scavenger, sulfur type antioxidant, benzotriazole compound, benzophenone compound etc.In addition, as releasing agent, can enumerate silicone based releasing agent etc., as silane coupling agent, can enumerate γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, γ-methacryloxypropyl methyl dimethoxysilane, gamma-amino propyl trimethoxy silicane, γ-glycidoxypropyltrime,hoxysilane etc.
The addition of tensio-active agent and silane coupling agent, be preferably 0～20 mass parts with respect to whole polymerizable monomer 100 mass parts, the addition of oxidation inhibitor, free radical scavenger, UV light absorber, releasing agent, anti-coloring agent, static inhibitor, fluorescence dye, dyestuff, pigment and spices etc. is preferably 0～2 mass parts respectively with respect to whole polymerizable monomer 100 mass parts.
Above-mentioned polymerization-curable composition is solidified and make the method for cured article there is no particular limitation.The various compositions of each set amount suitably can be mixed, be mixed with polymerization-curable composition of the present invention, be cured by thermopolymerization and/or photopolymerization then.At this moment, also can use thermal polymerization and/or Photoepolymerizationinitiater initiater as required.
As thermal polymerization, can enumerate for example peroxidation isobutyryl (10 hours half life temperatures: 33 ℃), peroxidation 2,4-dichloro-benzoyl (54 ℃), the adjacent chlorobenzoyl (54 ℃) of peroxidation, peroxidation two-3,5, the peroxidation diacyl of 5-trimethyl acetyl (60 ℃), lauroyl peroxide (61 ℃), benzoyl peroxide (72 ℃), chloro benzoyl peroxide (75 ℃) and so on; 2,4,4-tri-methyl-amyl new decanoate ester peroxide (41 ℃), α-cumyl new decanoate ester peroxide (38 ℃), tert-butyl hydroperoxide neodecanoic acid ester (47 ℃), the new capronate of tert-butyl hydroperoxide (54 ℃), t-butylperoxy pivarate (56 ℃), 1,1,3,3-tetramethyl butyl peroxidation-2-ethylhexanoate (64 ℃), t-amyl peroxy 2-ethylhexanoate (70 ℃), tert-butyl hydroperoxide 2-ethylhexanoate (74 ℃), tert-butyl hydroperoxide isobutyrate (78 ℃), di-tert-butyl peroxide six hydrogen terephthalate (83 ℃), tert-butyl hydroperoxide-3,5,5-tri-methyl hexanoic acid ester (100 ℃), tert-butyl hydroperoxide acetic ester (103 ℃), the peroxyester of tert butyl peroxy benzoate (105 ℃) and so on; Two-3-methoxy butyl peroxyization, two carbonic ethers (43 ℃), two-2-ethylhexyl peroxy dicarbonate (44 ℃), two (4-tert-butylcyclohexyl) peroxy dicarbonate (44 ℃), diisopropyl peroxydicarbonate (45 ℃), tert-butyl hydroperoxide sec.-propyl carbonic ether (97 ℃), 1, the peroxycarbonates of two (the tert-butyl hydroperoxide carbonyl oxygen base) hexanes (97 ℃) of 6-, two (tert-butyl hydroperoxide carbonic ether) (97 ℃) of glycol ether and so on; The dialkyl of dicumyl peroxide (117 ℃) and so on; 1,1-di-tert-butyl peroxide-3,3,5-trimethyl-cyclohexane (95 ℃), 1,1-cyclohexane di-tert-butyl peroxide (97 ℃), 2,2-two (tert-butyl hydroperoxide) butane (102 ℃), 4,4-di-tert-butyl peroxide n-butyl pentanoate (110 ℃), 2, the ketal peroxide of two (4,4-di-tert-butyl peroxide cyclohexyl) propane (92 ℃) of 2-and so on; The ketone peroxide of methylethyl ketone peroxide (105 ℃) and so on; 2,2 '-Diisopropyl azodicarboxylate (64 ℃), 2,2 '-azo two (2, the 4-methyl pentane nitrile) (52 ℃), 2, the azo-compound of two (2-methylbutyronitrile) (67 ℃) of 2 '-azo and so on.
These thermal polymerizations can use separately, also can multiplely be used in combination, particularly be that thermal polymerization more than 50 ℃ is when being used in combination with the thermal polymerization of 50 ℃ of 10 hours half life temperature less thaies and 10 hours half life temperatures, can improve the polymerization degree, obtain the also high lens of photochromic characteristic excellence and hardness and intensity (toughness), preferred from this respect.In addition, particularly be that thermal polymerization more than 50 ℃ is when being used in combination with the thermal polymerization of 50 ℃ of 10 hours half life temperature less thaies in the above-mentioned peroxyester and 10 hours half life temperatures, can further improve the polymerization degree, obtain photochromic characteristic more excellent and hardness and the also higher lens of intensity (toughness), most preferably from this respect.If the particularly preferred combination of illustration, then can enumerate tert-butyl hydroperoxide neodecanoic acid ester (47 ℃) and 1,1,3, the combination of the combination of the combination of 3-tetramethyl butyl peroxidation-2-ethylhexanoate (64 ℃), tert-butyl hydroperoxide neodecanoic acid ester (47 ℃) and tert-butyl hydroperoxide 2-ethylhexanoate (74 ℃), tert-butyl hydroperoxide neodecanoic acid ester (47 ℃) and t-amyl peroxy 2-ethylhexanoate (70 ℃).
There is no particular limitation for the usage quantity of these thermal polymerizations, fully carry out from making polymerization, and the viewpoint of remaining excessive thermal polymerization in the cured article is set out, with respect to whole polymerizable monomer 100 mass parts, be preferably 0.001～10 mass parts, be preferably 0.01～3 mass parts especially.Moreover, when the thermal polymerization of 50 ℃ of 10 hours half life temperature less thaies of combination and 10 hours half life temperatures are thermal polymerization more than 50 ℃, its usage quantity with respect to whole polymerizable monomer 100 mass parts is: the former 0.01～5 mass parts, the latter's 0.001～0.5 mass parts, more preferably the former 0.1～3 mass parts, the latter's 0.01～0.3 mass parts, further preferred the former 0.5～1.5 mass parts, the latter's 0.03～0.15 mass parts.
In addition; as Photoepolymerizationinitiater initiater; can enumerate for example bitter almond oil camphor, benzoin methyl ether, bitter almond oil camphor butyl ether, benzophenone, methyl phenyl ketone, 4; 4 '-dichloro benzophenone, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl methyl ketone acetal, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-isopropyl thioxanthone, two (2; 4; the 6-trimethylbenzoyl) phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-2; 4,4-tri-methyl-amyl phosphine oxide.
There is no particular limitation for the usage quantity of these Photoepolymerizationinitiater initiaters, fully carry out from making polymerization, and the viewpoint of remaining excessive Photoepolymerizationinitiater initiater in the cured article is set out, with respect to whole polymerizable monomer 100 mass parts, be preferably 0.001～10 mass parts, be preferably 0.01～3 mass parts especially.
Moreover thermal polymerization and Photoepolymerizationinitiater initiater can be distinguished use separately, also can use both simultaneously.But all the total amount of polymerization starter is 0.001～10 mass parts with respect to whole polymerizable monomer 100 mass parts.
Below, to the compound method of this polymerization-curable composition and used the manufacture method of the cured article of this polymerization-curable composition to be described in more detail.
The compound method of this polymerization-curable composition does not have special qualification, can enumerate for example following compound method: at first with two sense polymerizable monomers, 10～80 quality % of above-mentioned formula (1) expression, multifunctional polymerization monomer 1～15 quality % of above-mentioned formula (2) expression and polymerizable monomer 5～89 quality % in addition fully mix, thereby obtain polymerizable monomer composition 100 mass parts, then add 0.001～5 mass parts photochromic compound and carry out abundant stirring and dissolving, add again by having 2,2,6, photostabilizer 0.001～0.5 mass parts that the compound of 6-tetramethyl--4-piperidyl skeleton constitutes also fully mixes.Moreover, also can adopt will be by having 2,2,6, photostabilizer 0.001～0.5 mass parts that the compound of 6-tetramethyl--4-piperidyl skeleton constitutes adds photochromic compound 0.001～5 mass parts and carries out additive method such as abundant stirring and dissolving and mix in advance after polymerizable monomer mixes.
Also there is no particular limitation for using this polymerization-curable composition to make the method for cured article, below a example of method when for example using thermal polymerization describe.
At first, in this polymerization-curable composition, add above-mentioned initiator and stirring.Whipping temp and the time of this moment are 0～40 ℃, 0.1～300 minute.Then, hinder the molten oxygen of depositing of polymeric, under reduced pressure outgas in order to remove.The decompression degree of this moment and degassing time be 760mmHg following, 0.1～300 minute.Be injected in the space that forms by 2 sheet glass moulds and gasket or adhesive tape.At this moment, not necessarily use strainer, but by below 10 microns, preferred below 3 microns, the preferred especially strainer below 1 micron injects, and can access the extra high cured article of intensity (toughness), therefore more preferably.Moreover, about gasket, can use various materials, but viewpoint from easy acquisition, cost, and the high viewpoint of quality such as the tracing ability excellence during from polymerization shrinkage, thermotolerance height, preferably with ethylene-vinyl acetate copolymer, wherein vinyl acetate content is that 10～20% ethylene-vinyl acetate copolymer, polyolefin elastomer are as material.
Then, the operation that adopts heat to make the composition of casting carry out polymerizing curable is described.There is no particular limitation for polymerization time and temperature, but high and as the cured article of the good moldability of lens (no texture, peel off etc. bad) in order to obtain hardness and intensity (toughness), preferably slowly heats up from low temperature and carry out polymerization lentamente.If the preferred polymerizing curable condition of illustration, can enumerate through comprising (1) thus by in the operation that keeps making in 1～48 hour its gelation below 40 ℃, (2) thus then make the method for cured article with being warming up to the series of processes that makes its solidified operation, (3) more than 80 ℃ thereby then reach the operation below 30% in 2～24 hours at the survival rate that keeps more than 80 ℃ making curing proceed to polymerization starter in 1～10 hour.Moreover, even increase the operation that is cooled to preset temperature any problem can not appear more yet.Wherein, the survival rate R of polymerization starter is the calculated value of being calculated by following formula.
R＝e
-Kd·s
Wherein,
K
d＝A·e
-Ea/RT
A: each inherent frequency factor (unit: hr of polymerization starter institute
-1)
Ea: each inherent activation energy (unit: kJ/mol) of polymerization starter institute
R=8.314 * 10
-3(unit: kJ/mol/K)
T=(273.15+ centigradetemperature) (unit: K)
S: the time (unit: hr)
Moreover above-mentioned survival rate is to carrying out the whole operations of polymeric and carry out integration and calculating.
The deficiency of time of above-mentioned operation (1) has problems on the formability as lens in the time of 1 hour sometimes.That is, produce texture, peel off etc. bad.But also can form the also poor cured article of intensity (toughness).In addition, the deficiency of time of above-mentioned operation (2) can have problems on the formability as lens in the time of 2 hours too, and (toughness) the also poor cured article that forms intensity sometimes.In addition, the deficiency of time of above-mentioned operation (3) forms the cured article of hardness, intensity inequality in the time of 1 hour sometimes.In addition, surpass under 30% the situation, not only can form the cured article of intensity difference, also can produce the other problems that photochromic compound decomposes, photochromic characteristic reduces when using for a long time sometimes as lens at the survival rate of polymerization starter.
Moreover, if the particularly preferred polymerizing curable condition of illustration, then can be set forth in 33 ℃ keeps after 8 hours down, be warmed up to 40 ℃ with 4 hours, be warmed up to 55 ℃ with 4 hours again, be warmed up to 90 ℃ with 2 hours again, 90 ℃ keep 5 hours after, with the method (amounting to 24 hours) that was cooled to 80 ℃ in 1 hour; 33 ℃ down keep 4 hours after, be warmed up to 40 ℃ with 4 hours, be warmed up to 55 ℃ with 4 hours again, be warmed up to 90 ℃ with 2 hours again, 90 ℃ of maintenances after 2 hours, with the method (amounting to 17 hours) etc. that was cooled to 80 ℃ in 1 hour.
Behind the polymerizing curable, remove gasket or adhesive tape, between cured article and glass mold, insert blade etc. and make air admission, unload glass mold.In order to remove the polymerization strain, further annealed 0.1～10 hour down at 80～130 ℃, obtain the target cured article.
The cured article that polymerization-curable composition of the present invention is cured and obtains has the high advantageous feature of photochromic characteristic, hardness and intensity (toughness).Because this cured article has this advantageous feature, photochromism plastic lens substrate that optical article, particularly no-frame glasses are used especially therefore suits to be used as.When the cured article of polymerization-curable composition of the present invention was used for these purposes, the lens substrate that also can directly with forming process be suitable shape was as lens, but also can implement surface working as required and make lens.That is, can implement with silane coupling agent or be the processing that the hard paint of principal constituent carries out, adopt evaporation SiO with the colloidal sol composition of silicon, zirconium, antimony, aluminium, tin, tungsten etc.
2, TiO
2, ZrO
2Deng metal oxide film or be coated with the antireflection processing etc. of organic macromolecule membrane, thereby form lens.
As mentioned above, polymerization-curable composition of the present invention has following feature: even the prolonged preservation pigment can deterioration yet, have excellent photochromic characteristic, and can give to possess simultaneously the cured article of the enough anti-boring processing intensity that can be used for no-frame glasses.
Embodiment
By the following examples the present invention is described in more detail, but the present invention is not subjected to any qualification of these embodiment.Writing a Chinese character in simplified form and title of the compound that uses among the embodiment below at first is shown.
1, monomer
(I-1) two functional monomers of composition
BPE100:2, two (the 4-methacryloxy polyethoxye phenyl) propane (mean value of m+n is 2.6) of 2-
BPE200:2, two (the 4-methacryloxy polyethoxye phenyl) propane (mean value of m+n is 4) of 2-
BPE500:2, two (the 4-methacryloxy polyethoxye phenyl) propane (mean value of m+n is 10) of 2-
(I-2) polyfunctional monomer of composition
TMPT: trimethylolpropane trimethacrylate
TMPT3EO: ethoxylated trimethylolpropane trimethacrylate
(I-3) monomer of composition
The monomer that is equivalent to (A) composition
A200: Viscoat 335HP
A400: nine glycol diacrylates
PKA5009: molecular-weight average is 550 methoxy poly (ethylene glycol) allyl ethers
The monomer that is equivalent to (C) composition
4G: tetraethylene glycol dimethacrylate
Be equivalent to (A) composition and (C) monomeric monomer beyond the composition
M90G: molecular-weight average is 475 methyl ether polyethylene glycol methacrylate-styrene polymer
GMA: glycidyl methacrylate
α MS: αJia Jibenyixi
MSD: αJia Jibenyixi dipolymer
EB1830:6 official can the polymerizability polyester oligomer
2, photochromic compound
Chromene 1: the compound of following structure.The fade transformation period of this compound in ethylene glycol dimethyl ether (EGDME) solution is 0.4 minute.
Chromene 2: the compound of following structure.The fade transformation period of this compound in ethylene glycol dimethyl ether (EGDME) solution is 0.3 minute.
Chromene 3: the compound of following structure.The fade transformation period of this compound in ethylene glycol dimethyl ether (EGDME) solution is 0.2 minute.
3, photostabilizer
By having 2,2,6, the photostabilizer that the compound of 6-tetramethyl--4-piperidyl skeleton constitutes
LS765: two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate
LS770: two (2,2,6,6-tetramethyl--4-piperidyl) sebate
LS744:4-benzoyloxy-2,2,6, the 6-tetramethyl piperidine
In addition photostabilizer
TINUVIN571:2 (2H-benzotriazole-2-yl)-6-dodecyl-4-methylphenol
TINUVIN120:2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester
4, thermal polymerization
Tert-butyl hydroperoxide neodecanoic acid ester (half life temperature was 47 ℃ in 10 hours) (effective constituent is 75% product)
1 (half life temperature was 64 ℃ in 10 hours) (effective constituent is 90% product)
Tert-butyl hydroperoxide 2-ethylhexanoate (half life temperature was 74 ℃ in 10 hours) (effective constituent is 97% product)
Embodiment 1
50 mass parts BPE100,5 mass parts TMPT, 24 mass parts 4G, 5 mass parts A200,10 mass parts GMA, 5 mass parts α MS and 1 mass parts MSD are carried out thorough mixing.In the mixture that obtains, add 0.03 mass parts " chromene 1 " and 0.05 mass parts " LS765 " then, carry out thorough mixing, thereby make composition of the present invention.Then the composition that obtains was preserved 6 months in remaining 10 ℃ thermostat container.Through after the preservation period, from thermostat container, take out composition, add tert-butyl hydroperoxide neodecanoic acid ester (effective constituent be 75% product) and the 0.1 mass parts tert-butyl hydroperoxide 2-ethylhexanoate (effective constituent be 97% product) of 1.33 mass parts to it as thermal polymerization, carry out thorough mixing, after the degassing, the Mierocrystalline cellulose filter made device by 1 micron filters and is injected in the mold that constitutes by glass mold with by the gasket that ethylene-vinyl acetate copolymer forms.Descend maintenance after 4 hours at 33 ℃ it, be warmed up to 40 ℃ with 4 hours, be warmed up to 55 ℃ with 4 hours again, be warmed up to 90 ℃ with 2 hours again, kept 2 hours at 90 ℃, with being cooled to 80 ℃ (this moment, the calculated value of initiator survival rate was: tert-butyl hydroperoxide neodecanoic acid ester 0%, tert-butyl hydroperoxide 2-ethylhexanoate 2%) in 1 hour.After the polymerization, from the glass mold of mold, take out cured article, annealed 2 hours down at 110 ℃.Estimate photochromic characteristic and the strength characteristics and the xanthochromia degree of the cured article that makes then.Evaluation result is shown in Table 1.
Moreover the evaluation of the photochromic characteristic of cured article and strength characteristics and xanthochromia degree is undertaken by method shown below.
(1) strength characteristics
The cured article that use makes, behind the discoid test film of the thick 2mm of moulding, diameter 5cm Φ, as on the line of this discoid test film diameter respectively with the point of distance periphery 4mm as the center, be processed to form the hole of two diameter 2mm Φ with rig, in two borings that obtain, penetrate the stainless steel rod that diameter is 1.6mm Φ respectively, connect under the state of test film these two rods are separately fixed at tensile testing machine on the lower clamp, carry out tension test with the speed that 5mm/ divides, measure the tensile strength of this moment.
(2) xanthochromia degree
Use the color computer of ス ガ trier (strain) system, measure the yellow chromaticity (YI) that uses the cured article that the composition preserved 6 months makes in remaining 10 ℃ thermostat container and use the yellow chromaticity (YI of cured article of (preservation) composition manufacturing of new preparation
0), calculate xanthochromia degree (Δ YI)=(YI)-(YI
0).
(3) photochromic characteristic
On the cured article that obtains (thick 2mm, diameter 5cm's is discoid), xenon lamp L-2480 (300W) SHL-100 that makes with creek pine ホ ト ニ Network ス (strain), under 20 ℃ ± 1 ℃ with the beam intensity 365nm=2.4mW/cm of polymer surfaces
2, 245nm=24 μ W/cm
2, by エ ア ロ マ ス Off イ Le one (コ one ニ Application グ society system) irradiation 120 seconds, make its color development, measure the photochromic characteristic of above-mentioned test portion.Estimate each photochromic characteristic by the following method.
(i) maximum absorption wavelength (λ max): be the maximum absorption wavelength behind the color development obtained of the spectrophotometer (moment multichannel light electric explorer MCPD1000) that adopts (strain) big electronic industry to make.The tone of this maximum absorption wavelength during with color development is relevant.
(ii) color development concentration { ε (120)-ε (0) }: in above-mentioned maximum absorption wave strong point, carry out rayed after 120 seconds absorbancy { ε (120) } and above-mentioned ε's (0) is poor.This value is high more, and photochromism is excellent more.
[t (iii) fades the transformation period
1/2(min.)]: rayed is after 120 seconds, and when stopping rayed, the absorbancy at the above-mentioned maximum wavelength place of test portion is reduced to 1/2 required time of { ε (120)-ε (0) }.This time is short more, and the speed of fading is fast more, and photochromic characteristic is excellent more.
In addition, in contrast, will after preparation, carry out same polymerization at once, the cured article that makes is carried out same evaluation, but its result is basic identical with the composition of having preserved 6 months on whole projects by the same manner composition prepared.
Embodiment 2
20 mass parts BPE100,5 mass parts TMPT, 54 mass parts 4G, 5 mass parts A200,10 mass parts GMA, 5 mass parts α MS and 1 mass parts MSD are carried out thorough mixing.In the mixture that obtains, add 0.03 mass parts " chromene 1 " and 0.05 mass parts " LS765 " then, carry out thorough mixing, thereby make composition of the present invention.Then the composition that makes was preserved 6 months in remaining 10 ℃ thermostat container.Through after the preservation period, from thermostat container, take out composition, add tert-butyl hydroperoxide neodecanoic acid ester (effective constituent be 75% product) and 0.05 mass parts 1 of 1.33 mass parts to it as thermal polymerization, 1,3,3-tetramethyl butyl peroxidation-2-ethylhexanoate (effective constituent is 90% product), carry out thorough mixing, after the degassing, the Mierocrystalline cellulose filter made device by 1 micron filters and is injected in the mold that constitutes by glass mold with by the gasket that ethylene-vinyl acetate copolymer forms.Descend maintenance after 8 hours at 33 ℃ it, be warmed up to 40 ℃ with 4 hours, be warmed up to 55 ℃ with 4 hours again, be warmed up to 90 ℃ with 2 hours again, kept 5 hours at 90 ℃, (this moment, the calculated value of initiator survival rate was: tert-butyl hydroperoxide neodecanoic acid ester, 1,1 to be cooled to 80 ℃ with 1 hour, 3,3-tetramethyl butyl peroxidation-2-ethylhexanoate is 0%).After the polymerization, from the glass mold of mold, take out cured article, annealed 2 hours down at 110 ℃.By mode similarly to Example 1 prepared cured article is estimated then.Its result is shown in Table 1 in the lump.For present embodiment, also after compositions formulated, carry out polymerization immediately and test in contrast, but basic identical on the whole projects of evaluation result to the cured article that makes this moment with the composition of having preserved 6 months.
Embodiment 3～12 and comparative example 1～8
Except press shown in the table 1 change form, by similarly to Example 1 mode compositions formulated, preserve and polymerization, by mode similarly to Example 1 prepared cured article is estimated again.Its result is shown in Table 1 in the lump.The evaluation result of cured article is removed xanthochromia and is outside one's consideration all and has preserved 6 months basic identical.
From the embodiment of table 1 as can be known, the cured article that is made by polymerization-curable composition of the present invention has excellent photochromic characteristic, has the intensity that can be used for no-frame glasses, even when polymerization-curable composition is made cured article after 10 ℃ are down preserved 6 months, the xanthochromia degree is compared on quality when forming cured article without preservation also constant substantially.On the other hand, even such monomer is formed in the scope that is in the present invention's regulation shown in comparative example 1～6 as can be known, but do not contain the compound shown in the formula (3) as photostabilizer, if be cured after the prolonged preservation, the xanthochromia degree of cured article is big, do not carry out having taken place under light-struck state painted.In addition, shown in comparative example 7 and 8, the cured article that uses the polyfunctional monomer of two functional monomers, (I-2) composition of (I-1) composition and the composition beyond the scope that monomeric cooperation ratio (I-3) is in the present invention's regulation as can be known and obtain, do not obtain enough photochromic characteristics, or find that intensity reduces.
Table 1
| No | Polymerization-curable composition | ||||
| (I-1) composition (mass parts) | (I-2) composition (mass parts) | (I-3) composition (mass parts) | Photostabilizer (mass parts) | Photochromic compound (mass parts) | |
| Embodiment 1 | BPE100 50 | TMPT 5 | 4G/A200/GMA/αMS/MSD 24/5/10/5/1 | LS765 0.05 | Chromene 1 0.03 |
| Embodiment 2 | BPE100 20 | TMPT 5 | 4G/A200/GMA/αMS/MSD 54/5/10/5/1 | LS765 0.05 | Chromene 1 0.03 |
| Embodiment 3 | BPE100/BPE500 15/10 | TMPT 5 | 4G/A200/GMA/αMS/MSD 49/5/10/5/1 | LS765 0.05 | Chromene 1 0.03 |
| Embodiment 4 | BPE100 50 | TMPT 10 | 4G/A200/GMA/αMS/MSD 22/2/10/5/1 | LS765 0.05 | Chromene 1 0.03 |
| Embodiment 5 | BPE100/BPE500 5/30 | TMPT 5 | 4G/A200/GMA/αMS/MSD 39/5/10/5/1 | LS765 0.05 | Chromene 1 0.03 |
| Embodiment 6 | BPE100 50 | TMPT3E0 15 | 4G/A200/GMA/αMS/MSD 9/10/10/5/1 | LS765 0.05 | Chromene 1 0.03 |
| Embodiment 7 | BPE200 20 | TMPT 5 | 4G/M90G/GMA/αMS/MSD 44/15/10/5/1 | LS765 0.05 | Chromene 2 0.03 |
| Embodiment 8 | BPE200 40 | TMPT 5 | 4G/A200/GMA/αMS/MSD 34/5/10/5/1 | LS770 0.05 | Chromene 2 0.03 |
| Embodiment 9 | BPE100 50 | TMPT 5 | 4G/A200/GMA/αMS/MSD 24/5/10/5/1 | LS765 0.05 | Chromene 3 0.03 |
| Embodiment 10 | BPE100 20 | TMPT 5 | 4G/A200/GMA/αMS/MSD/EB1830 39/5/10/5/1/15 | LS765 0.05 | Chromene 1 0.03 |
| Embodiment 11 | BPE100 40 | TMPT 7 | 4G/A200/GMA/αMS/MSD/PKA5009 30/5/10/5/1/2 | LS765 0.05 | Chromene 1 0.03 |
| Embodiment 12 | BPE200 40 | TMPT 5 | 4G/A200/GMA/αMS/MSD 34/5/10/5/1 | LS774 0.05 | Chromene 2 0.03 |
Table 1 (continuing)
| No | Polymerization-curable composition | ||||
| (I-1) composition (mass parts) | (I-2) composition (mass parts) | (I-3) composition (mass parts) | Photostabilizer (mass parts) | Photochromic compound (mass parts) | |
| Comparative example 1 | BPE100 50 | TMPT 5 | 4G/A200/GMA/αMS/MSD 24/5/10/5/1 | - | Chromene 1 0.03 |
| Comparative example 2 | BPE100 20 | TMPT 5 | 4G/A200/GMA/αMS/MSD 54/5/10/5/1 | - | Chromene 1 0.03 |
| Comparative example 3 | BPE100/BPE500 15/10 | TMPT 5 | 4G/A200/GMA/αMS/MSD 49/5/10/5/1 | - | Chromene 1 0.03 |
| Comparative example 4 | BPE100 50 | TMPT 10 | 4G/A200/GMA/αMS/MSD 22/2/10/5/1 | - | Chromene 1 0.03 |
| Comparative example 5 | BPE100 50 | TMPT 10 | 4G/A200/GMA/αMS/MSD 19/5/10/5/1 | TINUVIN571 0.05 | Chromene 1 0.03 |
| Comparative example 6 | BPE100 20 | TMPT 5 | 4G/A200/GMA/αMS/MSD 57/2/10/5/1 | TINUVIN120 0.05 | Chromene 2 0.03 |
| Comparative example 7 | BPE100 50 | TMPT 20 | 4G/A200/GMA/αMS/MSD 9/5/10/5/1 | LS765 0.05 | Chromene 1 0.03 |
| Comparative example 8 | - | TMPT 15 | 4G/A200/GMA/αMS/MSD 64/5/10/5/1 | LS765 0.05 | Chromene 2 0.03 |
Table 1 (continuing)
| No | The pigment deterioration | Strength characteristics | Photochromic characteristic | |||
| Xanthochromia degree (Δ YI) | Tensile strength (Kgf) | λmax (nm) | Color development concentration | T in the cured article 1/2(branch) | T among the EGDME 1/2(branch) | |
| Embodiment 1 | -0.1 | 33 | 588 | 1.4 | 1.9 | 0.4 |
| Embodiment 2 | -0.3 | 26 | 588 | 1.3 | 2.0 | 0.4 |
| Embodiment 3 | -0.2 | 26 | 588 | 1.3 | 2.0 | 0.4 |
| Embodiment 4 | -0.2 | 20 | 588 | 1.4 | 1.8 | 0.4 |
| Embodiment 5 | -0.2 | 27 | 588 | 1.3 | 2.0 | 0.4 |
| Embodiment 6 | -0.3 | 32 | 588 | 1.4 | 2.1 | 0.4 |
| Embodiment 7 | -0.2 | 24 | 592 | 0.9 | 1.6 | 0.3 |
| Embodiment 8 | -0.1 | 32 | 592 | 1.0 | 1.6 | 0.3 |
| Embodiment 9 | -0.1 | 33 | 598 | 0.9 | 1.1 | 0.2 |
| Embodiment 10 | -0.3 | 28 | 588 | 1.3 | 2.0 | 0.4 |
| Embodiment 11 | -0.3 | 30 | 599 | 1.4 | 1.9 | 0.4 |
| Embodiment 12 | 0.0 | 32 | 592 | 1.0 | 1.6 | 0.3 |
Table 1 (continuing)
| No | The pigment deterioration | Strength characteristics | Photochromic characteristic | |||
| Xanthochromia degree (Δ YI) | Tensile strength (Kgf) | λmax (nm) | Color development concentration | T in the cured article 1/2(branch) | T among the EGDME 1/2(branch) | |
| Comparative example 1 | 0.7 | 33 | 588 | 1.4 | 2.0 | 0.4 |
| Comparative example 2 | 0.6 | 27 | 588 | 1.3 | 2.0 | 0.4 |
| Comparative example 3 | 0.6 | 28 | 588 | 1.3 | 2.0 | 0.4 |
| Comparative example 4 | 0.7 | 20 | 588 | 1.4 | 1.9 | 0.4 |
| Comparative example 5 | 0.5 | 21 | 588 | 1.4 | 1.9 | 0.4 |
| Comparative example 6 | 0.4 | 24 | 592 | 1.0 | 1.6 | 0.3 |
| Comparative example 7 | -0.2 | 10 | 588 | 1.3 | 1.9 | 0.4 |
| Comparative example 8 | -0.2 | 12 | 592 | 0.7 | 1.7 | 0.3 |
Claims (8)
1, polymerization-curable composition is characterized in that containing:
(I): by multifunctional polymerization monomer 1～15 quality % of two sense polymerizable monomers, 10～80 quality % of (I-1) following formula (1) expression, (I-2) following formula (2) expression and (I-3) above-mentioned (I-1) and (I-2) polymerizable monomer composition 100 mass parts formed of in addition polymerizable monomer 5～89 quality %
(II): photochromic compound 0.001～5 mass parts and
(III): by having 2,2,6, photostabilizer 0.001～0.5 mass parts that the compound of 6-tetramethyl--4-piperidyl skeleton constitutes,
In the formula, R
1And R
2Be hydrogen atom or methyl independently of one another, R
3And R
4Be the alkyl of hydrogen atom or carbon number 1～2 independently of one another ,-X-group be usefulness-O-,-S-,-S (=O)
2-,-C (=O)-O-,-CH
2-,-CH=CH-or-C (CH
3)
2The group of-expression, m and n are the integer that makes m+n=2～30 independently of one another,
In the formula, R
5Be hydrogen atom or methyl ,-R
6-group is usefulness-CH
2CH
2O-,-CH
2CH (CH
3) O-or-C (=O) CH
2CH
2CH
2CH
2CH
2The group that O-represents, R
7Be organic residue of 3～6 valencys, a is 0～3 integer, and b is 3～6 integer.
2, the described polymerization-curable composition of claim 1 wherein has 2,2,6, and the compound of 6-tetramethyl--4-piperidyl skeleton is the compound of following formula (3) expression,
In the formula, R
8, R
9Be hydrogen atom or methyl independently of one another, n is 5～12 integer.
3, polymerization-curable composition, it adds thermal polymerization 0.001～10 mass parts and forms with respect to claim 1 or 2 described polymerization-curable composition 100 mass parts.
4, the described polymerization-curable composition of claim 3, it is characterized in that:, add thermal polymerization 0.01～5 mass parts of 50 ℃ of 10 hours half life temperature less thaies and 10 hours half life temperatures and be thermal polymerization 0.001～0.5 mass parts more than 50 ℃ as thermal polymerization.
5, with claim 1 or 2 described polymerization-curable composition polymerizations and the cured article that obtains.
6, the manufacture method of the described cured article of claim 5 is characterized in that: make claim 1 or 2 described polymerization-curable compositions carry out thermopolymerization.
7, the manufacture method of the described cured article of claim 5, it is characterized in that: with respect to claim 1 or 2 described polymerization-curable composition 100 mass parts, add thermal polymerization 0.001～10 mass parts, through comprising that (1) is by in the operation that keeps making in 1～48 hour its gelation below 40 ℃, (2) thus then be warming up to and make its solidified operation more than 80 ℃ with 2～24 hours, (3) thus then solidify the series of processes that the survival rate that proceeds to polymerization starter reaches the operation below 30% keeping more than 80 ℃ making in 1～10 hour, carry out thermopolymerization.
8, the manufacture method of the described cured article of claim 7, it is characterized in that:, add thermal polymerization 0.01～5 mass parts of 50 ℃ of 10 hours half life temperature less thaies and 10 hours half life temperatures and be thermal polymerization 0.001～0.5 mass parts more than 50 ℃ as thermal polymerization.
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| PCT/JP2005/020782 WO2006051929A1 (en) | 2004-11-09 | 2005-11-08 | Polymerization-curable composition |
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| CN102812104B (en) * | 2010-04-01 | 2015-05-13 | 株式会社德山 | Photochromic curable composition |
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